Dimerization of Carboxylic Acids: An Equation of State Approach

Ioannis Tsivintzelis, Georgios Kontogeorgis, Costas Panayiotou

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Abstract

The association term of the nonrandom hydrogen bonding theory, which is an equation of state model, is extended to describe the dimerization of carboxylic acids in binary mixtures with inert solvents and in systems of two different acids. Subsequently, the model is applied to describe the excess enthalpies and the vapor-liquid equilibrium of relevant binary mixtures containing low molecular weight organic acids. The model sheds light on the interplay of intermolecular interactions through the calculation of the various contributions to the mixing enthalpies, namely from hydrogen bonding and non-hydrogen bonding (dipolar, induced polar or dispersive) interactions. According to model predictions, the acid molecules are so strongly associated that the addition of inert solvents to carboxylic acids with small carbon numbers at ambient temperature does not dramatically alter their degree of association. Consequently, the observed endothermic dissolution process is mainly attributed to the hindering of polar interactions. Furthermore, upon mixing of two carboxylic acids, the rearrangement of hydrogen bonds due to the formation of cross associating species results in an insignificant contribution to the heats of mixing due to the rather constant dimerization enthalpy that is revealed by the available experimental data for low molecular weight compounds.
Original languageEnglish
JournalJournal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Volume121
Issue number9
Pages (from-to)2153-2163
ISSN1520-6106
DOIs
Publication statusPublished - 2017

Cite this

@article{3b52713c20384f1e904fee2b8169d473,
title = "Dimerization of Carboxylic Acids: An Equation of State Approach",
abstract = "The association term of the nonrandom hydrogen bonding theory, which is an equation of state model, is extended to describe the dimerization of carboxylic acids in binary mixtures with inert solvents and in systems of two different acids. Subsequently, the model is applied to describe the excess enthalpies and the vapor-liquid equilibrium of relevant binary mixtures containing low molecular weight organic acids. The model sheds light on the interplay of intermolecular interactions through the calculation of the various contributions to the mixing enthalpies, namely from hydrogen bonding and non-hydrogen bonding (dipolar, induced polar or dispersive) interactions. According to model predictions, the acid molecules are so strongly associated that the addition of inert solvents to carboxylic acids with small carbon numbers at ambient temperature does not dramatically alter their degree of association. Consequently, the observed endothermic dissolution process is mainly attributed to the hindering of polar interactions. Furthermore, upon mixing of two carboxylic acids, the rearrangement of hydrogen bonds due to the formation of cross associating species results in an insignificant contribution to the heats of mixing due to the rather constant dimerization enthalpy that is revealed by the available experimental data for low molecular weight compounds.",
author = "Ioannis Tsivintzelis and Georgios Kontogeorgis and Costas Panayiotou",
year = "2017",
doi = "10.1021/acs.jpcb.6b10652",
language = "English",
volume = "121",
pages = "2153--2163",
journal = "Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "9",

}

Dimerization of Carboxylic Acids: An Equation of State Approach. / Tsivintzelis, Ioannis; Kontogeorgis, Georgios; Panayiotou, Costas.

In: Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, Vol. 121, No. 9, 2017, p. 2153-2163.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Dimerization of Carboxylic Acids: An Equation of State Approach

AU - Tsivintzelis, Ioannis

AU - Kontogeorgis, Georgios

AU - Panayiotou, Costas

PY - 2017

Y1 - 2017

N2 - The association term of the nonrandom hydrogen bonding theory, which is an equation of state model, is extended to describe the dimerization of carboxylic acids in binary mixtures with inert solvents and in systems of two different acids. Subsequently, the model is applied to describe the excess enthalpies and the vapor-liquid equilibrium of relevant binary mixtures containing low molecular weight organic acids. The model sheds light on the interplay of intermolecular interactions through the calculation of the various contributions to the mixing enthalpies, namely from hydrogen bonding and non-hydrogen bonding (dipolar, induced polar or dispersive) interactions. According to model predictions, the acid molecules are so strongly associated that the addition of inert solvents to carboxylic acids with small carbon numbers at ambient temperature does not dramatically alter their degree of association. Consequently, the observed endothermic dissolution process is mainly attributed to the hindering of polar interactions. Furthermore, upon mixing of two carboxylic acids, the rearrangement of hydrogen bonds due to the formation of cross associating species results in an insignificant contribution to the heats of mixing due to the rather constant dimerization enthalpy that is revealed by the available experimental data for low molecular weight compounds.

AB - The association term of the nonrandom hydrogen bonding theory, which is an equation of state model, is extended to describe the dimerization of carboxylic acids in binary mixtures with inert solvents and in systems of two different acids. Subsequently, the model is applied to describe the excess enthalpies and the vapor-liquid equilibrium of relevant binary mixtures containing low molecular weight organic acids. The model sheds light on the interplay of intermolecular interactions through the calculation of the various contributions to the mixing enthalpies, namely from hydrogen bonding and non-hydrogen bonding (dipolar, induced polar or dispersive) interactions. According to model predictions, the acid molecules are so strongly associated that the addition of inert solvents to carboxylic acids with small carbon numbers at ambient temperature does not dramatically alter their degree of association. Consequently, the observed endothermic dissolution process is mainly attributed to the hindering of polar interactions. Furthermore, upon mixing of two carboxylic acids, the rearrangement of hydrogen bonds due to the formation of cross associating species results in an insignificant contribution to the heats of mixing due to the rather constant dimerization enthalpy that is revealed by the available experimental data for low molecular weight compounds.

U2 - 10.1021/acs.jpcb.6b10652

DO - 10.1021/acs.jpcb.6b10652

M3 - Journal article

VL - 121

SP - 2153

EP - 2163

JO - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

JF - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

SN - 1520-6106

IS - 9

ER -